Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
  • C07F7/0838—Compounds with one or more Si-O-Si sequences
  • C07F7/0872—Preparation and treatment thereof
  • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
  • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
  • C07F7/0838—Compounds with one or more Si-O-Si sequences
  • C07F7/0872—Preparation and treatment thereof
  • C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F28—HEAT EXCHANGE IN GENERAL
  • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
  • F28D3/00—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium flows in a continuous film, or trickles freely, over the conduits

Definitions

• each substituent X is alkoxy, aroxy or halogen
• each substituent R is cyanoalkyl or carbamidoalkyl, having at least 3 carbon atoms in the chain between the nitrogen atom and the silicon atom
• each substituent R is alkyl, cycloalkyl, aryl, or neutrally substituted alkyl, cycloalkyl or aryl
• each substituent Y is a member bonded to two silicon atoms such as oxygen or B-substituted propylene radicals having the formulae at least one such substituent Y being a B-substituted propylene
• a is a positive number of at most 1 and n is a number greater than 1 and at most equal to 3, e.g.
• Z a complex boron-hydrogen compound having the formula H BZ in which Z is a ligand such as amines, alkali metal hydrides or alkaline earth metal hydrides, in the case of the said metal hydrides, if none of the substituents X is a halogen atom, then also in the presence of a boron halide,
• the invention relates to the hydrogenation of cyanoalkyl and carbamidoalkyl groups bound to silicon to produce primary amino compounds.
• the silicon compounds can be linear or cyclic, substituted siloxanes or silcarbanes as well as organo-silanes which contain, besides cyano-alkyl and carbamidoalkyl radicals, halogen atoms or alkoxy or aroxy radicals bound to silicon, which makes a further reaction of the hydrogenated products possible.
• the boron-hydrogen compound used for hydrogenation can be a borazane, i.e. amine-borine, or an alkali metal or alkaline earth metal borohydride.
• the borohydrides have to be combined with a boron halide the addition of which can be dispensed with if the silicon compound to be hydrogenated contains silicon-bound halogen.
• aminoalkyl-silicon compounds are produced by hydrogenation of organosilicon compounds containing carbon-bonded nitrogen in a process which comprises reacting an organo-silicon compound which may be a monomeric silane of the general formula RS iX t,
• each substituent X is an alkoxy or aroxy radical or a halogen atom
• each substituent R is a cyanoalkyl or carbamidoalkyl radical with at least 3 carbon atoms in a chain between the nitrogen atom and the silicon atom
• each substituent R is an optionally neutrally substituted alkyl, cycloalkyl or aryl radical, preferably methyl or phenyl, or a radical as defined for X
• a is a positive number of at most 1
• n is a number greater than 1 and at most equal to 3, at a temperature between 30 and 200 C., optionally in an inert solvent or dispersing agent, with a complex boron-hydrogen compound of the general formula H BZ, in which Z de notes an amine, or an alkali metal or alkaline earth metal hydride, in the last-mentioned cases, if none of the substituents X is simultaneously a halogen atom, in the presence of a boron halide, and solvolyzing the primary product by the addition of water, a dilute acid or an alkali metal hydroxide solution or an acohol, and recovering the end product by known methods.
• H BZ complex boron-hydrogen compound of the general formula H BZ, in which Z de notes an amine, or an alkali metal or alkaline earth metal hydride, in the last-mentioned cases, if none of the substituents X is simultaneously
• organosilanes to be hydrogenated are: p-cyanoethyl-trichlorosilane, fi-cyanoethyl-methyl-dichlorosilane, cyanopropyl-dimethyl-chlorosilane, ,B-cyanoethyl-diethoxy-chlorosilane, fi-cyanoethyl-trimethoxysilane, 'y-cyanopropyl-triethoxysilane, fi-cyanoethyl-methyldiethoxysilane, fi-carbamidoethyl-dimethyl-ethoxysilane.
• linear organo-siloxanes of the general formula include, for example: a,'y-bis-(dimethyl-chlorosilyl)-5- cyanopropane, or -bis-(dimethyl-ethoxysilyl)-B-carbamido-propane, and copolymers, e.g.
• Heterocyclic organo-siloxanes of the general formula R'nSiY are, for example: 4-cyano-2,2,6,fi-tetramethyl-1-oxa-2,6- disila-cyclohexane l ON 4 carbamido 2,2,6,6 tetramethyl 1 oxa 2,6 disilacyclohexane Hi CH:
• H BZ (
• Z may be a heterocyclic, optionally alkylated nitrogen base or a primary, secondary or tertiary amine whose substituents are uniform or different aliphatic, cycloaliphatic or aromatic hydrocarbon radicals.
• N-diethyl-borine amine can be used, for example, but N-trisubstituted borazanes, i.e. N-trisubstituted borine amines, e.g. N-trimethylborazane, i.e. N-trimethyl-borine amine, N-triethyl-bora- Zane, i.e. N-triethyl-borine amine, N-tripropyl-borazane,
• N-tripropyl-borine amine N-butyl-N-diethyl-bora- Zane, i.e. N-butyl-N-diethyl-borine amine, N-cyclohexyl- N-diethyl-borazane, i.e. N-cyclohexyl-N-diethyl-borine amine, and pyridine-borine, will be preferred because they are more readily available.
• a metal borohydride of the formula H BZ is used as hydrogenating agent, sodium borohydride is chiefly recommended, which is readily obtainable and easy to handle. If a boron halide, e.g. boron trifiuoride, is concurrently used, this can also be employed in the form of an addition compound, in particular one added on to an ether, such as tetrahydrofuran.
• Suitable inert solvents or dispersing agents for the reactants are aliphatic and aromatic hydrocarbons and ethers, such as tetrahydrofuran, tetrahydropyran and di-nbutyl ether.
• the process according to the invention is generally carried out under atmospheric pressure, but it is also possible to use nitrogen or hydrogen under increased pressure, for example the hydrogen which evolves during the process itself if borazanes, i.e. borine amines, are used.
• the heating in the first step of the process is carried out for about 1 to 5 hours.
• the subsequent solvolysis is brought about, for example, by the addition of a dilute mineral acid.
• the aminoalkyl-silicon compound is isolated from its salt thus formed, by the addition of a dilute alkali metal hydroxide solution and by extraction, for example with ether, the boron remaining in the aqueous phase in the form of boric acid or alkali metal borate.
• an alcoholysis will be carried out in those cases where an organo-silicon compound with a hydrolytically splittable bond is present, e.g. an alkoxysilane, and if a siloxane condensation is to be prevented in the process.
• the solvolysis is then brought about by means of an alcohol, for example methanol, and the boric acid ester thereby formed is separated by distillation from the product of the process.
• the hydrogenation can be carried out with an alkali metal or alkaline earth metal borohydride Without the addition of a boron halide. In this case, an exchange of the halogen atoms for hydrogen atoms takes place, in addition to the main reaction.
• the hydrogen-silicon compound thus formed can be converted into the corresponding alkoxy-silicon compound by subsequent alcoholysis.
• halogen atom are bound to one silicon atom, such as e.g. in fi-cyanoethyl-methyl-dichloro-silane
• hydrogenation by means of a metal borohydride leads to the formation of diborane as a secondary product, which can be combined in known manner with an amine, so that the process according to the invention is coupled with the production of borazanes, i.e. borine amines.
• the process can be varied in two Ways: either the halogen atoms of the silicon compound to be hydrogenated are removed in known manner by partial alcoholysis to such an extent that only one of them remains attached to the silicon atom and the hydrogenation is carried out only thereafter in the manner described above, or only a partial hydrogenation is carried out by means of an alkali metal borohydride so that, besides the formation of amino groups, only a partial exchange of halogen for hydrogen takes place.
• the subsequent solvolysis yields the hydrogenation product in the form of an amine-hydrohalide from which a polysiloxane with free amino groups can be obtained by means of an alkaline solution.
• Example 3 to the invention are suitable, for example, for the known application for the surface modification of glass, especially glass fibres, inorganic fillers and pigments, also for the production of surface-active agents, such as emulsifiers, and for the modification of synthetic resins.
• Example 1 89.4 grams (0.33 mol) 1,3-di-('y-cyanopropyD-tetramethyl-disiloxane are dissolved in 200 cc. tetrahydrofuran, and this solution is added to a suspension of 22 g. (0.58 mol, 15% excess) sodium borohydride in 100 cc. tetrahydrofuran. To this mixture there is further added dropwise a solution of 98 g. (0.7 mol, 5% excess) of the boron trifluoride/tetrahydrofuran addition product in 200 cc. tetrahydrofuran, and the reaction mixture is boiled under reflux fo one hour. After cooling, 100 cc. methanol and 20 cc.
• Example 2 30 grams (0.34 mol) of a,w('y-cyanopropyl)-polydi methyl-siloxane which contains 2.9 percent by Weight nitrogen and approximately corresponds to the above formula, are dissolved in 300 cc. tetrahydrofuran, and this solution is added to a suspension of 24 g. (0.64 mol, 25% excess) sodium borohydride in 100 cc. tetrahydrofuran. To this mixture there is further added dropwise a solution of 105 g. (0.75 mol, 10% excess) of the boron trifluoride/tetrahydrofuran addition product in 200 cc. tetrahydrofuran, and the reaction mixture is boiled under reflux for one hour.
• Example 4 6 grams (0.028 mol) 4 carbamido 2,2,6,6 tetramethyl-1-oxa-2,6-disila-cyclohexane are dissolved in 50 cc. tetrahydropyran, and this solution is added to a sus pension of 1.65 g. (0.043 mol) sodium borohydride in 20 cc. tetrahydrofuran. To this mixture there is further added a solution of 7.5 g. (0.054 mol) of boron trifluoride/tetrahydrofuran addition product in 50 cc. tetrahydrofuran, and the reaction mixture is boiled under reflux for 4 hours. The further procedure is the same as that described in Example 3, but only 100 cc.
• each of ether and hydrochloric acid are used.
• fractional distillation there are obtained 4 g. (about 70% of the theoretical amount) 4 aminomethyl 2,2,6,6 tetrarnethyl-l-oxa- 2,6-disila-cyclohexane with boiling point 45 C. at 0.4 mm.
• Hg and refractive index n 1.4521 which can be identified by the infra-red spectrum.
• Example 5 162 grams (1 mol) ('y-cyanopropyl-dirnethyl-chlorosilane are dissolved in 200 cc. tetrahydrofuran, this solution is added dropwise to a suspension of 45.5 g. (1.2 mol) sodium borohydride in 200 cc. tetrahydrofuran, and the reaction mixture is then boiled under reflux for 4 hours. After cooling, the precipitated sodium chloride is separated by filtration. Therein 85% of the chlorine used are determined by titration.
• Example 6 nm-om -suouomm 2Na01 213 011 4H1 162 grams (1 mol) 'y-cyanopropyl-dimethyl-chlorosilane are dissolved in 200 cc. tetrahydrofuran, this solution is added dropwise to a stirred suspension of 47 g. (1.25 mol) sodium borohydride in 300 cc. tetrahydrofuran, and the reaction mixture is boiled under reflux for 5 hours. The precipitated sodium chloride and the excess sodium borohydride are separated by filtration, the solvent is substantially evaporated from the filtrate and the residue taken up with 250 cc. ether.
• Example 7 168 grams (1 mol) ,B-cyanoethyl-methyl-dichlorosilane are dissolved in 200 cc. tetrahydrofuran, this solution is added dropwise to a suspension of 83 g. (2.2 mol) sodium borohydride in 200 cc. tetrahydrofuran, and the reaction mixture is boiled under reflux under an argon atmosphere for 4 hours. 101 grams (1 mol) triethylamine are then added and the mixture is filtered after cooling. In the filter residue dissolved in water, 90% of the chlorine used can be determined by titration.
• the residue after distillation consists of the hydrochloride of 'y-aminopropyl-methyl-dimethoxy-silane.
• Example 8 123 grams (0.057 mole) of a siloxane-silcarbane copolymer which contains 2.6 percent by weight nitrogen and, on average, approximately corresponds to the above formula, are dissolved in 250 cc. isopropylbenzene, 32 g. (0.28 mol) N-triethyl-borazane are added to this solution and the mixture is heated at a temperature between and C. for 2 hours. The solvent and the excess borazane are then evaporated by heating up to 110 C. at 2 mm. Hg and the highly viscous residue is decomposed with a mixture of 300 cc. methanol and 20 cc. water. The volatile components are distilled ofi, 300 cc.
• each substituent X is selected from the group consisting of alkoxy and aroxy radicals and halogen atoms
• each substituent R is a radical selected from the group consisting of cyanoalkyl and carbamidoalkyl, having at least 3 carbon atoms in a chain between the nitrogen atom and the silicon atom
• each substituent R is a radical selected from the group consisting of alkyl, cycloalkyl, aryl, and neutrally substituted alkyl, cycloalkyl and aryl
• each substituent Y is a member which is bonded to two silicon atoms and which is selected from the group consisting of an oxygen atom and beta-substituted propylene radicals having the formulae at least one
• said medium is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, linear aliphatic ethers, cyclic aliphatic ethers, and mixtures thereof.
• organosilicon compound is 'y-cyanopropyl-dimethyl-chlorosilane.
• organosilicon compound is p-cyanoethyl-methyl-dichlorosilane.
• organosilicon compound is 1,3-di-( -cyanopropyl)-tetramethyldisiloxane.
• organosilicon compound is u,w-di('y'-cyanopropyl)-polydimethylsiloxane having about 11 dimethyl siloxy units.
• organosilicon compound is 4-cyano-2,2,6,6-tetramethyl-l-oxa-2,6- disila-cyclohexane.
• organosilicon compound is 4-carbamido-2,2,6,6-tetramethyl-loxa-2,6-disila-cyclohexane.
• organosilicon compound is siloxane-silcarbane copolymer end stopped with trimethyl silyl groups and having about 20 dimethyl siloxy units separately interrupted by about 4 distinct groups each attached to adjacent silicon atoms.
• Example 3 the 4H" at the end should be 4H column 6 line 64, cancel the opening parenthesis before "(7-cyanopropy1-" column 7, line 40, "ZNaBH” should be -2NaBH column 8, line 35, "RaR' should be --RaR' Si0-- SIGNED AND SEALED MAY 1 91970 Edward M. Fletcher, Jr-

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• 1964
  • 1964-03-14 DE DEF42314A patent/DE1195753B/de active Pending
• 1965
  • 1965-03-03 BE BE660551D patent/BE660551A/xx unknown
  • 1965-03-05 FR FR8198A patent/FR1437493A/fr not_active Expired
  • 1965-03-09 GB GB994865A patent/GB1050305A/en not_active Expired
  • 1965-03-12 US US439477A patent/US3458553A/en not_active Expired - Lifetime

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